Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/04—Oxidation
  • C08C19/06—Epoxidation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule

Definitions

• This invention relates to a newclass of curable polymers containing-oxirane oxygen, to their method of manufacture, and to the cured resinous compositions produced.
• a variety of types of polymers containing oxirane oxygen are known, and some of these polymers have achieved wide and varied use due to the reactivity of their oxirane oxygen functionality with avariety of types of compounds.
• Each type of epoxy polymer (as oxirane containing resins are commonly called), has its particular uses, advantages and disadvantages. There is a continuing' need for improved epoxy polymers, particularly those of enhanced workability and versatility in the uncured state and of improved properties when cured.
• novel compositions of the present invention are oxirane containing resins which are epoxidized condensation products ofconjugated dienes with polyalkyl-aromatic compounds, wherein such condensation products contain an average of at least two molar equivalents of diene residue per molar equivalent of polyalkyl-aromatic residue.
• These new epoxy resins arecharacterized by a number of interesting and useful advantages, not only as formed, but in the cured compositions produced by cross-linking these resins by. reacting the epoxygroups with polyfunctional curing agents.
• These new epoxy resins may be produced to contain a relatively high oxirane oxygen content product, for which the viscosity may be adjusted to fall within a wide range, from very low to very high, thus providing an extremely versatile class of new epoxy resins.
• these resins are characteristically oflower viscosity, for a given molecular weight range and oxirane oxygen content, than corresponding epoxy polydiolefins, providing products ,of greatly enhanced utility ascompared With related types ofepoxy resins.
• the resins of this invention provide improvedworkability, enhanced wetting and impregnation of porous materials, better filling of voids and higher filler loading in molding and casting applications, longer pot life before curing, and lower exotherm during cure.
• cross-linking agents of which a wide variety-may be used, new products of exceptional utility and versatility are obtained, useful in lamina-ting, casting, potting and coating applications.
• a polymeric condensation product is prepared by reacting a conjugated diolefin with a polyalkyl-aromatic compound.
• the diene and the polyalkyl-aromatic compound are condensed or copolymerized so that the resulting product has an average composition of at least two residues of the diene reactant for each one of polyalkylaromatic compound, said diene residues reacting primarily on the alkyl side chain of the polyalkyl-aromatic compound, to produce an essentially linear product.
• Methods for preparing this type of polymer are well known in the art.
• the conjugated diolefin employed herein preferably contains four to eight carbon atoms and includes such dienes as butadiene, isoprene, 2,3-dimethylbutadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene-1,3,
• polyalkyl-aromatic compounds may be employed, to provide products having particular properties, and/and for reasons, of economy and. availability.
• the alkyl substituents on the aromatic ring preferably contain one to three carbon atoms in each alkylchain, although chains of greater length may be used if desiredto produce products having particular properties.
• polymethyl aromatic hydrocarbons such as the isomeric xylenes, mesitylenes and methylated naphthalenes.
• the condensation ofthe diene with. the polyalkylaromatic compound is accomplished by known techniques.
• double bonds derived from condensation of the diene with itself and with the alkyl groups on the aromatic.
• the novel epoxidized copolymers which are the subject of this invention contain at least 1% by weight of epoxy oxygen, and preferably about 4 to 10% epoxy oxygen by weight.
• Epoxy copolymers containing. a relatively high concentration of epoxy oxygen tend to be extremely viscous, especially in the higher molecular weight ranges; but this may actually be desired for special applications, such ascoatings. In practice, the maximum epoxy oxygen content of these resins is about 12% by Weight.
• viscosity of the epoxy copolymer dependson such factors as the molecular weight and viscosity of the unepoxidized copolymer and the degree of epoxidation; and, of' course, the viscosity of a particular epoxy, resin may be. lowered. by the use of solvents or diluents.
• the novel epoxy resins provided herein are believed to have a structure consisting of a central polyalkyl-aromatic residue having a multiplicity of condensed diene. unitsattached thereto and polymerized onto some. or all of the alkyl groups, and in which a portion of the. residual unsaturated-bonds in the diene units has been converted tov epoxy groups.
• the diene residues presentin the copolyrners of this invention are believed to be coupled partly by 1,4-linkages, which provide residual. unsaturated bonds in the body of the copolymer chains, and partly by 1,2-linkages, which provide residual external unsaturated bonds, in the form of vinyl groups on the copolymer chains. Therefore, these epoxidized copolymers contain both internal and external epoxy groups, and usually some residual olefinic unsaturation, the amount of residual unsaturation varying inversely with the degree of epoxidation,
• the ratio of the diene and the polyalkyl-aromatic starting materials may be varied within wide limits. It is preferred that at least two moles of diolefin be reacted per mole of polyalkybaromatic compound. When less than a two molar excess of diolefin is reacted, a portion of the product consists of low molecular weight condensates and pos sibly unreacted polyalkyl-arorn-atic starting material. Although such low molecular weight products may actually be desired for special applications, or to lower the Patented Apr. 12, 1-966- viscosity of higher molecular weight product, in general it is preferred that the product contain an average of at least two moles of diolefin per mole of polyalkyl-aromatic compound.
• the beneficial aspects of the instant invention are marked when about to 50% by weight of the final product is derived from the polyalkyl-aromatic compound. This is roughly equivalent to a 2 to 18 molar excess of diene o-ver aromatic compound. At substantially more than an 18 molar excess of diene the properties of the condensation product approach those of the polydiene itself, at the expense of many of the advantages of the instant invention. But within the stated limits, the ratio of the diene and the aromatic compound may be varied over a considerable range, depending on the particular properties desired in the expoxidized and cured products.
• the condensation is conveniently accomplished using a finely divided alkali metal catalyst, such as sodium, potassium, or lithium, or a mixture of alkali metals, or their alloys, at elevated temperatures.
• Alkali metal hydride catalysts are also effective in this reaction, and other catalysts for the preferential reaction of the olefin with the alkyl side chain rather than the aromatic ring.
• sodium is a preferred catalyst. Rapid conversion is obtained using a catalytic amount of finely divided sodium, in mass or solution polymerization, by known techniques for sodium catalyzed polymerization.
• sodium may be dispersed in an inert hydrocarbon diluent such as benzene or kerosene, in the presence or absence of a dispersing agent.
• the catalyst may be suspended in a polyalkyl-aromatic compound such as xylene, for ultimate incorporation into the polymeric structure. Useful methods of preparing catalysts for this reaction are well known in the art.
• the amount of polymerization catalyst employed may be varied, depending on the desired properties of the product, but normally is in the range of 0.1 to 10 parts of catalyst per 100 parts of diene monomer. Excellent results are normally obtained in the range of 3 to 5 parts catalyst per 100 parts of diene monomer.
• the catalyst may be dispersed in an inert solvent for the reactants, such as benzene, aliphatic hydrocarbons such as petroleum ether, decalin and the like. in general, it is convenient to employ solvents boiling in the range of 50150 C., although the boiling range of the solvent is not critical. Normally a solvent is used which'can be distilled or otherwise stripped from the reaction mix after polymerization. As previously stated, bulk polymerization in the'absence of added solvent or diluent may also be carried out, whereby the catalyst is dispersed in the polyalkyl-aromatic compound, which compound is then incorporated into the product during the polymerization reaction.
• the condensation reaction generally occurs at temperatures above about 75 C., the reaction temperature being selected to produce condensation products in the desired molecular weight range.
• the reaction is conveniently carried out in an autoclave, by introducing therein the starting hydrocarbons and the catalyst, and heating the reaction mixture to a temperature between about 75 and 200 C. for several hours, preferably while agitating the mixture.
• the mixture is cooled or otherwise quenched, and catalyst, diluent and unreacted monomers if any are removed, all by standard procedures.
• the catalyst is conveniently removed by washing with water or acid, and volatile materials are readily distilled.
• the resulting polymeric condensation product of the diene with the polyalkyl-aromatic compound is an oily to viscous liquid. It is primarily linear in structure and contains residual olefinic unsaturation, normally characterized by an iodine number in the range of about 250 to 400.
• the molecular weight of these condensation products is generally in the range of about 250 to 1000, corresponding to a viscosity range of about 0.5 to 10 poises at zero shear and 25 C. Should it be desired to prepare polymers for epoxidation to a relatively low epoxy content, polymers of higher viscosity and molecular weight may be desired, and are readily prepared by conventional modifications of these standard polymerization procedures.
• Aliphatic, aromatic and inorganic peracid-s, salts of the peracids, peroxides and hydroperoxides are the most common of the effective epoxidizing agents.
• lower aliphatic peracids such as performic, peracetic, perpropionic and perbutyric are preferred reagents.
• the epoxidation reaction may be carried out using a preformed peracid, or the peracid may be formed in the reaction medium, generally by adding hydrogen peroxide to an alpihatic acid or anhydride medium.
• Peracids may be prepared in any known way, such as is described in Organic Syntheses, Coll.
• An epoxidation catalyst may also be employed, such as a small amount of a strong acid, or a cation exchange resin as described by Gall and Greenspan, Ind. Eng. Chem. 47, 147-8 (1955). Normally a solvent for the copolymer, such as chloroform, benzene, xylene and the like, is present during the epoxidation.
• the amount of available active oxygen employed in the epoxidation reaction is that necessary to produce the desired oxirane-oxygen content of the epoxidized copolymer. In practice, an excess of active oxygen above that theoretically required may be used, to compensate for losses due to decomposition of the oxidant and/ or ring opening of the oxirane groups on the polymer.
• tough, infusible resins which are useful in a variety of' ways, as in the potting and encapsulating of electronic assemblies and in other casting applications, as adhesives, in decorative and structural laminates, in protective coatings, andin many other resinous applications, either alone or in combination with other resins.
• Useful curing agents herein include polycarboxylic acids and anhyd-ries, polyamines, combinations of anhydrides and polyols, anhydride-polyol adducts, polymercaptans, urea-formaldehyde adducts, Lewis acids and Lewis acid complexes, and many more simple and complex structures containing more than one group which reacts with oxirane oxygen. Further, these epoxy polymers may be extended with vinyl and allyl monomers and cured with the curing agents described above in the presence of peroxide catalysts, to produce homogeneous, hard, tough, infusible products halving particular properties for particular uses.
• Polycarboxylic anhydrides which may be used to react with and cure the novel epoxy polymers of this invention, to form novel, ⁇ cross-linked resinous products, include aliphatic dicarboxylic acid anhydrides, such as succinic anhydride, glutaric anhydride, propylsu-ocinic anhydride, methylbutylsuccinic anhydride, hexylsuccinic anhydride, pentenylsuccinio anhydride, ocetenylsuccinic anhydride, nonenylsuccinic anhydride, alpha, betadiet-hylsu ccinic anhydride, maleic anhydride, chloromaleic anhydride, dichloro'maleic anhydride, itaconic 'anhydride, citraconic.
• aliphatic dicarboxylic acid anhydrides such as succinic anhydride, glutaric anhydride, propylsu-ocinic anhydride, methylbutyl
• cycloaliphatic dicarboxylic acid anhydrides such as hexahydrophthalic anhydride, hexa'chlorophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrachlorphthalic anhydn'de; hexachloroendomethylenetetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride; aromatic dicar boxylic acid anhydrides, such as phthalic anhydride, 4- nitrophthalic anhydride, 1,2-naphthalic anhydride, 1,8- naphthalic anhydride, 2,3-naphthalic anhydride; tetracarboxylic acid dianhydrides, such as 1,2,4,5-benzenetetracarboxylic dianhydride; polymeric dicarboxylic acid anhydrides, such as those prepared by the autocondensation of dicarboxylic acids, for example
• dicarboxylic acid anhydrides include the Diels-Alder adducts of maleic acid and aliphatic compounds having conjugated double bonds.
• Preferred polycarboxylic acid anhydrides are the aliphatic hydrocarbon dicarboxylic acid anhydrides, the cycloaliphatic hydrocarbon dicarboxylic acid anhydrides and the aromatic hydrocarbon dicarboxylic acid anhydrides.
• Polycarboxylic compounds which may be used in the compositions of this invention are compounds which contain two or more free carboxy groups per molecule.
• Representative polycarboxylic compounds are polycarboxylic acids including such dicarboxylic acids as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, alkylsuccinic acids, alkenylsuccinic acids, ethylbutenylsuccinic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, ethylidenemalonic acid, isopropylidenemalonic acid, allylmalonic acid, muconic acid, alpha-hydromuconic acid, betahydromuconic acid, diglycolic acid, dilactic acid, dithioglycolic acid, 4-amyl-2,5-
• polycarboxylic compounds which can be used are compounds containing ester groups and two or more carboxyl groups and can be aptly termed polycarboxy polyesters of polycarboxylic acids, such as those listed above, or the corresponding anhydrides of said acids, withpolyhydric alcohols.
• polycarboxy polyesters as used herein, is meant polyesters containing two or more free carboxy group per molecule.
• These polycarboxy polyesters can be prepared by known condensation procedures, employing mole ratios favoring greater than equivalent amounts of polycarboxylic acid or anhydride.
• the amount of polycarboxylic acid or anhydride, employed in the esterification reaction should contain more carboxy groups than are required to react with the hydroxyl groups of the polyhydric reactant.
• it is prefe'rab'le to use hydrocarbon dicarboxylic acids or anhydrides.
• Adducts of anhydrides and polyols useful as curing agents include bis and tris half esters of polyols with aliphatic and aromatic polycarboxylic acid anhydrides, prepared by reacting one molar equivalent of 6 anhydride with each equivalent of polyol hydroxyl group; and acid-terminated polyesters, obtained by reacting anhydrides with polyols using molar ratios of anhydride to polyol greater than one.
• Polyhydric alcohols which can be employed in preparing these polycarboxy polyesters include dihydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-p-ropylene glycol, 1,3-propylene glycol, dipropylene glycols, tripropylene glycols, polyoxyethylene glycols, polyoxypropylene glycols, 1,2-butylene glycol, 1,4-butylene glycol, pentane-1,5-diol, pentane-2,4-diol, 2,2-dimethyltrimethylene glycol, hexane-1,4-diol, hexane-1,5-diol, hexane-1,6- diol, hexane-2,5-diol, .S-methylpentane-1,5-diol, 2-methylpentane-2,5-diol, 3-methylpentane-2,5-
• Additional polyhydric alcohols useful in making polycarboxy polyesters can be prepared by the reaction of epoxides, e.g., diglycidyl ethers of 2,2-propane bis-phenol, and reactive hydrogen-containing organic compounds, e.g., amines, polycarboxylic acids, polyhydric compounds and the like.
• epoxides e.g., diglycidyl ethers of 2,2-propane bis-phenol
• reactive hydrogen-containing organic compounds e.g., amines, polycarboxylic acids, polyhydric compounds and the like.
• a dihydric, trihydric or tetrahydric aliphatic or oxa-aliphatic alcohol e.g., 1,3-dioxa-aliphatic alcohol.
• the mole ratios in which the polycarboxylic acid or anhydride is reacted with polyhydric compounds are those which provide polyesters having more than one earboxy group per molecule; and in the case of trifunctional and tetrafunctional reactants in the esterification reaction, the mole ratios of the respective reactants must of course be such as to avert gelation during esterification.
• the polycarboxy polyesters described above are thus obtained by condensing, in accordance with known procedures, a polyhydric compound and a palycarboxylic acid or anhydride.
• This condensation reaction may be conducted, for example, -by heating the reactants to a temperature within the range of C. to 200 C., with or without an acidic catalyst. Water formed in the condensation reaction may be removed by distillation. The course of the reaction may be followed by making acid number determinations, and the reaction can be stopped when a suitable polycarboxy polyester has been obtained.
• the acids and anhydrides useful for this invention may be liquids or solids although, for convenience, acids and anhyd-rides which are liquids, low melting solids and highly soluble solids are preferred.
• High-melting slightly soluble acids and anhydrides such as trimellitic acid, pyromelletic d-ianhydride and diglycolic acid may --be used by intimately mixing with the resin and curing at an elevated temperature, which causes reaction and solution of curing agent.
• Acidic and basic catalysts may not be necessary to carry out curing although they may be employed, as desired, to promote a more rapid cure. These catalysts can be added to the polymerizable compositions in amounts of .001 to weight percent based upon the total weight of compositions.
• Basic catalysts which may be employed include pyridine, aniline, benzyldimethylamine, benzyltrimethylammonium hydroxide, dilute alkali hydroxides, and the like.
• Suitable acidic catalysts include sulfuric acid, phosphoric acid, perchloric acids, and Friedel-Crafts catalysts, e.g., stannic chloride, zinc chloride, ferric chloride, boron trifluoride, aluminum chloride, and the like.
• polycarboxylic acid anhydrides may be used in combination with polyols, in the absence of prior esterification of these components.
• Useful polyols and anhydrides for such systems are those previously described.
• the reaction rate is usually increased and the fluidity of the resin formulation is improved, as is the wettability of fillers and laminating fabrics. This use of polyols also usually causes a decrease in brittleness of the cured products.
• the amount of anhydride used should be at least equivalent to the amount of aliphatic polyol used.
• equivalent amount is meant equivalent number of reactive groups; thus a simple anhydride contains two reactive groups, and a glycol contains two reactive groups. It is usually preferred to use excess anhydride equivalents over polyol equivalents for best results.
• equivalent amounts of anhydride and polyol are used the rate of cure is lower, but may be accelerated with an acid catalyst.
• excess polyol is used, a reasonable rate of cure may still be obtained by using an acid catalyst, but the properties of the products are in general inferior.
• the total amount of combined anhydride plus polyol requiredfor optimum properties in the cured epoxy polymer composition depends both on the degree of epoxidation of the polymer and on the particular curing combination used.
• one epoxide equivalent of epoxy polymer that is, the amount of epoxy polymer containing one atom of epoxy oxygen, requires a total amount of anhydride plus polyol containing at least one equivalent of reactive groups.
• a simple anhydride and a simple glycol each contains two reactive groups, and thus each contains two equivalents of reactive groups-a simple anhydride plus a simple glycol, combined, contain a total of four reactive groups.
• anhydride component of this curing system a wide variety of unsaturated polycarboxylic anhydrides containing reactive double bonds may be used, alone or in combination with each other or with saturated anhydrides.
• Typical reactive unsaturated anhydrides include maleic, monosubstituted maleic such as chloromaleic and citraconic, itaconic, bicyclo-(2,2,l)-5heptene- 2,3-dicarboxylic, bicyclo (2,2,1) 5 methyl 5 heptene2,3-dicarboxylic and many other unsaturated auhydrides having reactive double bonds, of varied structure and properties.
• compositions having specific curing characteristics and cured properties.
• compositions may be prepared where as much as of the anhydride component consists of a saturated anhydride, or an anhydride containing relatively unreactive double bonds, since the presence of even 5% of reactive double bonds in the anhydride contributes substantially to the improved properties of the product.
• Typical anhydrides in combination include succinic, dodecenylsuccinic, octenylsuccinic, diand tetrachlorop hthalic, tetrahydrophthalic, hexahydrophthalic, dichlor-omaleic, pyromellitic, bicyclo-(2,2,1)-5-hetene-1,4,5,6,7,7 hexaohlor 2,2 dicarboxyli-c, and many others.
• the corresponding dior polycarboxylic acids may be used in place of all or a portion of the anhydrides to increase the rate of cure. Again, substituents such as halogen or other groups may be incorporated for special applications.
• a polyol is employed with the unsaturated anhydride, it is preferably an aliphatic polyhydric alcohol, as previously discussed, including the glycols and glycol ethers, and long chain diols of straight and branched chains, which chains may contain aromatic rings, such as xylylene glycol and dimethylxyly-lene glycol.
• Higher polyols such as glycerol, pentaerythritol, polyallyl alcohol, sorbitol, trimethylolbenzene and many others may also be used, as well as a large number of other dihydroxy and polyhydroxy compounds.
• Unsaturated polyols such as 2-butene-1,4-diol, dihydroxycyclopentene and tetrahydroxycyclohexene are also useful herein, and if the unsaturated polyol contains reactive double bonds this polyol may be used in combination with or in place of the unsaturated function of the an hydride.
• Substituents such as halogen, nitro, aimido or other functional groups may also be incorporated to impart particular properties to the prodnet.
• the free radical initiating agent may be any agent which is stable below the curing temperature, but which liberates free radicals into the system under the curing conditions.
• These free radical initiators are of the same type as is normally used in the catalysts of free radical polymerization reactions, the most common of which are peroxygen compounds, such as aliphatic, aromatic and inorganic peracids, salts and esters of the peracids, peroxides and hydroperoxides. It is preferred herein to use organic peroxy compounds which are compatible with and soluble in the other components of the curing system. Examples of such peroxides include t-butyl perbenzoate,
• the decomposition temperatures of such free radical initiators may be in the broad range of about 25 to 200 0., since the anhydride or polyol-anhydride cure systems are readily formulated as to be reactive throughout this range. Most of the peroxides listed above are active in the preferred range of 75 175 C., since this is a convenient temperature range for obtaining completely cured products within a reasonable time. If curing is to be effected in two or more staages by progressively increasing the temperature, a combination of two or more appropriately selected free radical initiators may be used.
• the decomposition of the peroxide is promoted by the use of various well-known additives, typically acids or amines such as phosphoric acid, cobalt naphthenate, dimethyl aniline and boron trifiuoride. 'I he decomposition temperature is, in fact, progressively lowered during the curing step by acid formed during the reaction.
• the amount of free radical initiator used may vary over a wide range, and from 0.01% to of peroxide, by weight of total curing agent may be used. In general, excellent results are obtained in a preferred range of about 0.2% to 2% of peroxide. When less than an effective amount of peroxide is present, the results are the same as if the anhydride-polyol system alone were used. There is no advantage to the use of excess peroxide, and in fact large excesses should be avoided, to avoid contamination of the polymer with residues of the peroxide.
• vinyl and allyl monomers may be reactive vinyl and allyl monomers, often but not necessarily used in the typical anhydride/polyol systems previously described.
• Useful vinyl and allyl monomers are typified, for example, by xinyl aromatic monomers such as styrene, alpha-methyl styrene, vinyl toluene, divinyl benzene and the like; cyclic compounds such as dicyclopentadiene; unsaturated esters such as methyl methacrylate; common vinyl monomers such as acrylonitrile; and allyl monothem such as triallyl phosphate, diallyl phthalate, dimethallyl m-aleate, and many other reactive monomers.
• any particular curing mechanism it appears as if the vinyl or allyl monomer cop'olymerizes with the unsaturated anhydride, and that this copolymerization is accompanied by interaction with the residual double bonds in the epoxy polymer to form a terpolymer based on addition polmerization, which polymerization'occurs concurrently with condensation interaction among the anhydride, polyol if any, and epoxy groups.
• the amount of vinyl monomer which is employed in the curing formulation depends somewhat on the degree of residual unsaturati'on in the particular epoxy resin, and on the specific polymerization characteristics of the unsaturated anhydride. Best results are generally obtained in the range of about 30 to 60' parts vinyl or allyl monomer per 100 parts epoxy polymer.
• the peroxide used in the curing formulation should be .so selected that it does not decompose at the temperatures at which it is desired to prepare and, if necessary, store the composition before curing.
• An inhibitor may be used to prevent premature thermal or photochemical initiation of the polymerization.
• the curing reaction is preferably carried out at low to moderate temperatures, to facilitate control of the reaction rate, which increases with increased temperature.
• a useful procedure is to allow the coposition to stand fora brief period at temperatures between about 0 C. and C., and then to raise the temperature to about 75 C. to 175 C. to complete the reaction.
• the epoxidized diene-polyalkyl aromatic condensation product of this invention may also be cured by reacting these epoxy products with polyhydric phenols, such as resorcinol, catechol, hydroquinone, 4,4'-dihydroxy diphenyl sulfone, the alkyl bisphenols such as 4,4'-dihydroxy diphenyl propane, the A or B stage phenol-aldehyde condensates, and the like.
• the phenolic hydroxyl groups may be present on one or more aromatic rings, and the molecules containing them may also contain other functional groups reactive with oxirane oxygen.
• the polyhydric phenols may be selected for their ability to crosslink among themselves with or without such added ingredients as hexamethylenetetramine, thereby augmenting the thermosetting reaction between the phenols and the epoxy containing polymer.
• the selection of the curing agent depends somewhat on the ultimate intended use.
• the epoxy polymer and the polyhydroxy phenol should form a pourable mixture at room or moderately elevated temperature; thus the polyhydric phenols used should either be liquid at ordinary temperature, or possess a relatively low melting point to permit mixing at room temperature or moderately elevated temperature, or be soluble in the epoxy polymer.
• the polyhydric phenols used are therefore those soluble in the solvent from which the coating is to be made.
• the amount of polyhydric phenol used for curing the epoxy condensation product depends on the oxirane oxygen content of the epoxy polymer, the particular polyhydric phenol used, and the properties desired in the thermoset resinous product. Where complete reaction is desired, one equivalent weight of the epoxy polymer, that is, the weight of epoxy condensation product containing 16 grams of oxirane oxygen, is reacted with one equivalent weight of the polyhydric phenol.
• the equivalent weight of the polyhydric phenol is the molecular weight of the polyhydric phenol divided by the number of phenolic hydroxyl groups. In general, from 10 to of the amount of polyhydric phenol theoretically required for complete reaction, is used to cure the novel epoxy resins of this invention.
• polyfunctional amines are primary or secondary amines, since these amines contain active hydrogen atoms, and are exemplified by such compounds as ethylene diamine, propylene diamine, diethylene triamine, tetraethylene pentamine, m-phenylene diamine, iminobis-propylamine, triethylene tetramine, methyl piperazine, dimethyl piperazine, and many other simple and complex polyfunctional amines, which may also contain functional groups in addition to amino groups, both to react with the epoxy polymer and to impart particular properties to the cured product.
• polyamines which either are liquid at ordinary temperatures or possess a relatively low melting point; and in the case of coating resins the polyamines ll used are those soluble in the solvent from which the coating is made.
• the amount of primary or secondary polyamines used for curing these epoxy polymers depends, as before, on the degree of epoxidation of the diene-polyalkylaromatic condensation polymer, and the particular polyamine used.
• amine curing formulations may be catalyzed, if desired, by small amounts of such catalysts as strong carboxylic acids, Lewis acid, phenols, tertiary amines and quaternary ammonium compounds, to provide shorter cure cycles and rapid development of mechanical strength.
• catalysts for amine cure include benzyldimethylamine, triethylamine, boron trifiuoride, phenol, glycolic acid, and many others.
• the resins of this invention may also be cured with urea-formaldehyde and substituted urea-formaldehyde resins, normally of low molecular weight.
• Urea-formaldehyde resins containing amino and hydroxyl groups are usually used in solution because of their high viscosities.
• These urea-formaldehyde resins usually require elevated temperatures for complete reaction with the epoxy-containing diene-aromatic resins of this invention, and are of special usefulness in forming coatings.
• More soluble, substituted urea-formaldehyde resins such as low molec ular weight ethylurea-formaldehyde resins, may be used without a solvent to provide useful cured products without the need for elevated curing temperatures. These resins are of substantial interest and utility as film-forming agents for coating applications.
• Lewis acids are also usable as curing agents, both free Lewis acids and Lewis acid complexes where an unshared pair of electrons from a nitrogen or oxygen-containing compound are complexed to the unfilled octet of the Lewis acid.
• the complexed Lewis acids are used in applications requiring reduced activity or extended pot lives where the cure formulations must be storable for long periods at low temperatures prior to use.
• the Lewis acid complexes decompose on heating to release the Lewis acids.
• Suitable complexes are boron trifluoride-etherates, boron trifiuoride-triethanol amine, aluminum chloride-piperidine, zinc chloride-monoethanol amine, zinc chloride-acetone complexes, and many other complexes of this type.
• Lewis acids both free and complexed, tend to cause self-condensation of the epoxy groups even at low concentrations. These materials are also of value, when used in small amounts, as catalysts for amine, acid, and anhydride curing formulations. In general, between 0.1 and 10 parts by weight of Lewis acid or Lewis acid complex is used per 100 parts of resin, although, for some applications requiring very short or very long cure cycles or in applications requiring relatively soft or very hard cured products, larger or small amounts may be employed. 1
• Polymercaptans containing a multiplicity of hydrosulfide groups are also reactive with the epoxy resins of this invention.
• these materials react somewhat slowly at room temperature and require curing at elevated temperatures or catalysts such as Lewis acids, glycolic acid, butylphosphate, stannous octoate, benzyldimethylamine, or other acidic or basic catalysts, for complete reaction.
• catalysts such as Lewis acids, glycolic acid, butylphosphate, stannous octoate, benzyldimethylamine, or other acidic or basic catalysts, for complete reaction.
• the cured products thus obtained, because of their sulfide linkages, show excellent adhesion to most metals, plastics and rubbers. A particularly useeither alone or in combination with other resins.
• 12 ful curing agent of this type is a liquid Thiokol polysulfide rubber.
• the amount of curing agent employed is based on that theoretically required to react with the epoxy groups in the polymer, and may vary within wide limits, depending on the amount of epoxy oxygen present, on whether or not complete reaction and cross-linking is required, and on the particular properties desired in the cured product.
• any two or more curing components may be premixed prior to blending into the resin, which itself may contain one or more cure agents.
• one or more cure agents may be blended with the resin prior to addition of any remaining cure agents.
• the curing time varies of course with the starting materials and the curing temperature.
• a reaction period of one to six hours at 25200 C. is sufiicient, although longer periods are sometimes required for maximum properties, especially at temperatures approaching room tem perature.
• charring may occur due to the exothermic nature of the curing reactions.
• the products of this invention are useful in a variety of ways, as in potting and encapsulating of electronic assemblies and other casting applications, in laminates and in protective coatings and other resinous applications, They are particularly useful in applications requiring superior weatherability and chemical resistance. They may be combined with glass fibers or other reinforcing agents, with plasticizers, flexibilizers, fillers, extenders, pigments and dyes, and many other materials, for specific applications. Exemplified below are certain specific embodiments of this invention, designed to illustrate but not to limit the novel methods and compositions described herein. All parts are by weight unless otherwise indicated. Mechanical properties were determined according to standard ASTM procedures.
• Example 1 A mixture of 400 grams of meta-xylene, 300 ml. of benzene and 200 ml. of sodium dispersion, prepared by dispersing about 30% by weight of sodium in benzene, was charged under nitrogen to an autoclave, sealed and heated to C. The. gases were vented, and to the autoclave was sharged a total of 1000 parts of. butadiene added over a period of twohours. 'six hours of reaction, a viscous product was obtained under 15 p.s.-i.g. The temperature was maintained at about 90 C., and the pressure at 10 to 15 p.s.i.g., during addition of the butadiene. After all the butadiene had been added the reaction was continued for 30.
• the reaction mixture was cooled to room temperature and quenched into excess water.
• the aqueous phase was discarded, and the oil phase was neutralized, washed, and stripped of solvent.
• the residue was a fluid copolymer oil having a viscosity at 25 C. of 75 centistokes, or about 70 centipoises, and an iodine number of 313.
• the copolymer yield was about 1400 grams.
• Example 2 One hundred parts of the epoxidized eopolymer of Example 1 were mixed with 31 parts of maleic anhydride and four parts of propylene glycol and heated for two hours at 100 C. A transparent tack-free rubbery composition was produced having considerable toughness and elasticity. Further postcuring at 155 C. for 24- hours resulted in a clear, light amber-colored, rigid product having an ASTM heat distortion temperature of 98 C. and a Rockwell M hardness of 100.
• Example 3 A mixture of 750 parts of benzene, 16 parts of sodium and 131 parts of a commercial mixed xylene containing 25% ortho xylene, 46% meta xylene, 20% para xylene and 9% ethylbenzene was heated in an autoclave to 90 C. and to it was added a total of 326 parts of butadiene under 15 p.s.i.g. After the butadiene had been absorbed as revealed by a drop in pressure to about 3 p.s.i.g. the reaction mixture was quenched and neutralized, the oil phase was separated off, washed with water and expoxidized at 65 C.
• Example 4 One hundred parts of the epoxidized copolymer of Example 3 were blended with 30parts of styrene, 40.3 parts of maleic anhydride, 5.2 parts of ethylene glycol and 0.65 part of dicumyl peroxide. A rubbery tack-free product resulted after heating for 3 hours. at: 80 C. After an additional three hours at 155 C.,. the ASTM fiexural and tensile strengths of the product were 17,720 p.s.i. and 8,000 p.s.i., respectively, and the Rockwell M hardness was 1.05.
• Example 6 Seventy parts of the epoxidized product of Example 3 were blended with 30: parts of styrene, then mixed with 0.5 part of dicumyl peroxide and 40 parts of a viscous liquid adduct prepared by reacting 30 parts of maleic anhydride with 30 parts of diethylene glycol at C. for three hours. This mixture was precuredat 80 C. for 'two hours to a rubbery tack-free state, and then'postcured at C. for three hours; A hard, toughproductwas obtained having a Rockwell M' hardness of 109 and flexural and tensile strengths of 17,000 p.s.i. and 8,890 p.s.i., respectively. 7
• Example 7 A- copolymer of butadiene and x ylene was prepared as in Example 3 using 16 parts of sodium,, 180 parts of butadiene and 66 parts of commercial mixed xylenes. After workup and removal of solvent a clear red copolymer oil was obtained having a viscosity at 25 C. of 3.0-poises and an iodine number of 323. One hundred parts of this copolymer were dissolved in 200 parts of chloroform and epoxidized at 30-40 C. by adding,.over a periodof'about 4 hours, parts of'40% peracetic acid to'which had been added 20 grams ofsodium acetate as buffer. The reaction mixture was washed with water, and the-solvent removed by distillation from the oil phase. The product had an oxirane oxygen content of 6.0% and a viscosity of 2,000 poises at 25 C.
• Example 8 One hundred parts of theepoxidized product of Example 7 were cured with 35 parts, of'ci-traconic anhydride, 5 parts of 2,3-butylene glycol and 0.5 part of dicumyl peroxide. The time required at 80 C. to produce a non-tacky rubbery state was two hours; The rubbery product was then postcured at 155 C. for 3 hours to form a product having a Rockwell M hardness of 104 and flexural and tensile strengths of 14,690 psi. and 7,730 p.s.i., respectively. The. heat distortion temperature after 24 hours postcure was 156 C.
• Example 9 Butadiene, 954 parts, was copolyme'rized as in Example 1 with 200 parts of. para-xylene.
• the solvent-free copolymer product was a dark red oil' having an iodine number. of 337. and a viscosity at 25 C. of 18 poises.
• One hundred parts'of this eopolymer were dissolved in 100 parts of benzene and epoxidized at 65 C. using ten parts of formic acid, two parts of phosphoric acid and 80' parts of 50 percent hydrogen peroxide;
• the epoxidized product was a very viscous-orange-colored oil containing 7.4 percent oxirane oxygen and having a viscosity at 25 C. of about 27,000 poises.
• Example 10 One hundred grams of the epoxidized product. of Example 9 were cured. using 100 parts of alpha-phenethylsuccinic anhydrideand four parts of; glycerol. Upon heating this mixture for one hour at 100 C., a very adhesive tough, rubbery product was obtained which'hardened to a very tough, hard, infusible product when postcured at 155 C. for an additional three hours.
• Example 11 A mixture of 100 parts of meta-xylene, 500 parts of benzene and 12 parts of sodi'um dispersed in an equal weight of kerosenewas heated'ih an autoclave to 90" C., and to this was charged a total of 200'parts ofliquid isoprene'. After 1.5 hours at 8590'C., the reaction mixture was quenched into excess water and the aqueous phase was discarded. The oil' phase was neutralized, washed free of inorganic salts and stripped free of solvent. The residue was a fluid copolymer: oil of'about 90 centipois'es viscosity at 25 0., having an iodine number' of 222. One. hundred parts of this copolymer, as a 40% solution in benzene, were mixed with 10 parts of formic under p.s.i.g. pressure.
• Example 12 One hundred parts of the epoxidized copolymer ofExample 11 were mixed with 24 parts of 'meta-phenyle'nediamine and cured by heating for four hours at 105 C. A hard, tough solid was produced, which exhibited marked adhesion to metals.
• Example 13 Butadiene, 230 parts, was copolymerized as in Example 3 with 200 parts of commercial mixed xylenes, to give a yellow copolymer oil having a viscosity of 1 poise at 25 C. and an iodine number of 317.
• One hundred parts of this copolymer were dissolved in an equal weight of benzene and epoxidized at 65 C. by slowly adding a solution of ten parts of formic acid, one part of phosphoric acid and 90 parts of 50% hydrogen peroxide, over a period of 2 hours. The resulting product was cooled and neutralized; the oil phase was separated, washed with water, dried and distilled free of solvent.
• the solventfree epoxidized copolymer was a light yellow liquid having an oxirane oxygen content of 7.9% and a viscosity of 42 poises at 25 C.
• Example 14 Fifty parts of the product of Example 13 were mixed with 25 parts of meta-xylylenediamine and two parts of phenol and heated for 24 hours at 120 C. A very hard, strong infusible solid product was produced, which formed very tenacious adhesive bonds when cured in contact withglass, aluminum, steel, wood or concrete.
• Example 15 One hundred parts of the epoxidized copolymer of Example 13 were mixed with 20 parts of triethylenetetramine and three parts of glycolic acid. This mixture was degassed, and heated for 15 hours at 80 C., at which time a tough, rubbery, product was obtained which post- Example 16
• One hundred parts of -the epoxidized copolymer of Example 13 was blended with 60 parts of styrene. To this blend was mixed one part of cumene hydroperoxide and 100 parts of a 2/ 1 molar adduct of maleic anhydride and dipropylene glycol, prepared by reacting the maleic anhydride and dipropylene glycol at 100 C. for three hours.
• the product had a flexural strength of 20,100
• Example 17 A mixture of 300 parts of ortho-xylene, 1500 parts of benzene and 50 parts of sodium. dispersed in an equal weight of benzene was heated inan autoclave to 90 C., and to it was added a totalof 1000 parts of butadiene mixture wasquenched into excess water and the aqueous phase was discarded. The oil phase was neutralized,
• This mixture was gelled at room temperature overnight, and was then postcured at 150 C. for four After the butadiene had been absorbed, as indicated by a drop in pressure, the reaction viscosity at 25 C.
• One hundred parts of this copolymer were dissolved in an equal weight of benzene and mixed with 10 parts. of formic acid and 1 part of sulfuric acid. This mixture was agitated, warmed to C., and parts of 50% aqueous hydrogen peroxide were added to it over a period of one and one half hours. The reaction mixture was then cooled, washed and neutralized. The oil phase was separated off, washed with water, dried and distilled free of solvent to yield a viscous liquid containing 5.7% oxirane oxygen and having a viscosity of 9,840 poises at 25 C.
• Example 18 Fifty parts by weight of the epoxidized product of Example 17 were mixed with 15 parts of maleic anhydride and three parts of 2,3-butylene glycol and spread over parts of glass fiber cloth. The resin-coated cloth was assembled into a laminate and heated for 15 hours at C., to produce a very tough, hard, chemically resistant laminate characterized by excellent adhesion of resin to glass.
• Example 19 Mesitylene and butadiene were copolymerized in the ratio of one mole mesitylene for four moles of butadiene, following the procedure of Example 1.
• One hundred parts of the resulting fluid copolymer were dissolved in an equal weight of benzene, and mixed with 10 parts of formic acid and 1 part of sulfuric acid. The mixture was agitated, warmed to 65 C., and 80 parts of 50% aqueous hydrogen peroxide were added over a period of one and one half hours.
• the reaction mixture was cooled, washed and neutralized, the oil phase was separated, washed, dried and distilled free of solvent, to produce a yellow viscous liquid analyzing 6.23% oxirane oxygen and having a. viscosity of 530 poises at 25 C.
• Example 20 One hundred parts of the product of Example 19 were cured by heating with 65 parts of bicyclo-(2.2.1)-5- Butadiene was copolymerized with durene in the ratio of six moles of butadiene to one mole of durene, following the procedure of Example 1.
• Example 22 One hundred parts of the product of Example 21 were cured by heating with 80 parts of hexahydrophthalic anexcellent adhesion to glass.
• Example 23 ture was held at 65 C. for an additional four hours, then cooled and the product separated, washed and distilled One hundred parts of the epoxy product'of Example 23 were mixed with 100 parts of phthalic anhydride and heated at 100 C. for 30 hours. A dark colored tough product was obtained having excellent adhesive prop erties.
• Example 25 A mixture of'300 parts of dimethylnaphthalene, 1000 parts of benzene and 53 parts ofsodium dispersed in an equal Weight of benzene was heated in an autoclave to 90 C. A total of 700 parts of butadiene was charged, under 10-15 pounds per square inch gauge pressure. After the bu tadiene had been absorbed the reaction "mixture was quenched into excess water and the aqueous phase was discarded. The oil phase was neutralized, washed free of inorganic salts and stripped free of solvent. The residue was a viscous copolymer oil.
• Example 26 When 100 parts of the product of Example 25 were mixed with 20 parts of diethylene triamine and parts of resorcinol and heated for 5 hours at 100 C., a hard, tough resin was obtained which showed excellent adhesion to a variety of plastics and metals.
• Example 27 One hundred parts of a butadiene-xylene copolymer prepared as in Example 1 were dissolved in 200 parts of toluene and mixed with 25 parts of sodium acetate. This mixture was agitated and heated to 50 C. Two hundred and thirty parts of 39% peracetic acid were added over a period of 1 hour. The reaction mixture was held at 50 C. for an additional 1 hour, and then cooled and neutralized. The oil phase was separated, washed with water, dried and distilled free of solvent, to yield an almost colorless oil containing 9.0% oxirane oxygen and having a viscosity of 50 poises at 25 C.
• Example 28 One hundred parts of the product of Example 27 were mixed with 100 parts of alpha-phenethylsuccinic anhydride, 4 parts propylene glycol and 0.5 part benzyldimethylamine. After heating for 3 hours at 100 C., the product had cured to a non-tacky, machinable rubber. After an additional 4 hours at 155 C., the product had a flexural strength of 16,460 p.s.i., tensile strength of 9,640 p.s.i. and Rockwell (M) hardness of 87.
• M Rockwell
• Example 29 Fifty parts of the epoxidized copolymer of Example 27 were blended with 50 parts of styrene, 100 parts of a condensate prepared by heating 2 moles of maleic anhydride with 1 mole of diethylene glycol at 120 C. for 2 hours, and 2 parts of cumene hydroperoxide. After heating for three hours at 100 C. and 4 hours at 155 C. the cured product had a flexural strength of 20,430 p.s.i. and tensile strength of 10,760 p.s.i., and Rockwell (M) hardness of 111.
• M Rockwell
• Example 30 One hundred parts of the epoxidized copolymer of Example 27 were blended with 20 parts of diethylene triamine and 5 parts of resorcinol. After curing two 18 hours at 100 C. and 4 hours at 155 C., the product exhibited a fiexural strength of 19,920 and a tensile strength of 10,270 p.s.i., of 101.,
• Example 31 A mixture of 400 grams of meta-xylene, 1000 ml. of benzene, and 40 grams of finely divided lithium dispersed in anequal weight of isoctane, was charged under nitrogen to an autoclave, sealed and heated to C. The gases we're vented, and to the autoclave was charged a total of 1000- parts of butadiene under 15 p.s.i.g. The temperature was maintained at about 90" C., and the pressure at-10 to 15 p.s.i .g., during. addition of the butadiene. After all the butadiene had been added the reaction was continued for one hour at 90-95 C., and the reaction mixture was cooled to room temperature and quenched into excess water.
• the aqueous phase was discarded, and the oil phase was neutralized, washed and stripped of solvent.
• the copolymer thus obtained was dissolved in an equal weight of chlorobenzene and epoxidized with 1000 grams of 42% peracetic acid at 30-35 C.
• Example 32 One hundred parts of the epoxidized product of Example 31 were heated with 50 parts of glycolic acid at C. for 4 hours. A hard, strong, chemically resistant resin was obtained.
• Example 33 One hundred parts of the epoxidized copolymer prepared in Example 30 were heated at 125 C. with 75 .parts of adipic acid and two parts of dibutyl phosphate. After six hours a tough, flexible product was produced, which showed excellent resistance to thermal shock.
• Example 34 Fifty parts of the epoxidized product of Example 30 were mixed with six parts of a 1.1 molar complex of boron trifluoride and triethanol amine. This mixture was stable for several days at room temperature, during which time it did not change appreciably in viscosity. Upon heating this mixture to about C., a rapid, exothermic reaction was observed which produced a hard, tough adhesive product.
• Example 35 One hundred parts of the epoxidized product of Example 30 were mixed with 100 parts of alphaphenethylsuccinic anhydride and four parts of aluminum trichloride-acetone complex. After standing at room temperature for about five minutes, a rapid exothermic reaction set in and the entire mass quickly hardened into a tough, infusible solid.
• polymer'of claim '1 wherein the polyalkylsubstituted aromatic compound is a .polymethyl naphthalene.
• polyalkylsubbstituted aromatic compound is durene.
• polyalkylsubstituted aromatic compound is lutidine.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
• Epoxy Resins (AREA)

Priority Applications (6)

Applications Claiming Priority (1)

Publications (1)

Family

ID=22373335

Family Applications (1)

Country Status (5)

Cited By (1)

Families Citing this family (1)

Citations (8)

• 0
  • BE BE618835D patent/BE618835A/xx unknown
  • NL NL279785D patent/NL279785A/xx unknown
• 1961
  • 1961-06-16 US US117512A patent/US3245977A/en not_active Expired - Lifetime
• 1962
  • 1962-05-16 GB GB18773/62A patent/GB990427A/en not_active Expired
  • 1962-06-15 CH CH724562A patent/CH433766A/de unknown

Patent Citations (8)

Also Published As

Similar Documents